Mixed-ionomer electrode

ABSTRACT

A membrane electrode assembly includes a membrane, an anode catalyst layer and a cathode catalyst layer. The anode catalyst layer is on a first side of the membrane and the cathode catalyst layer is on a second side of the membrane, wherein the second side of the membrane is opposite the first side of the membrane along a first axis. The cathode catalyst layer includes agglomerates formed of a catalyst support supporting catalyst particles, an agglomerate ionomer and an inter-agglomerate ionomer. The agglomerate ionomer surrounds the agglomerates and the inter-agglomerate ionomer is in regions between the agglomerates surrounded by the agglomerate ionomer. The agglomerate ionomer is different than the inter-agglomerate. Methods to produce the catalyst layer are also provided.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. patent application Ser. No.13/818,366, filed Feb. 2, 2013, which is a 371 of internationalApplication No. PCT/US2010/046313, filed Aug. 23, 2010, where eachapplication is incorporated herein by reference in its entirety.

BACKGROUND

A proton exchange membrane fuel cell (PEMFC) includes an anode, acathode and a proton exchange membrane (PEM) between the anode andcathode. In one example, hydrogen gas is fed to the anode and air orpure oxygen is fed to the cathode. However, it is recognized that othertypes of fuels and oxidants can be used. At the anode, an anode catalystcauses the hydrogen molecules to split into protons (H⁺) and electrons(e⁻). The protons pass through the PEM to the cathode while theelectrons travel through an external circuit to the cathode, resultingin production of electricity. At the cathode, a cathode catalyst causesthe oxygen molecules to react with the protons and electrons from theanode to form water, which is removed from the system.

The anode catalyst and cathode catalyst are commonly formed of platinumsupported on carbon. The platinum catalyst is only active when it isaccessible to protons, electrons and the reactant (i.e., hydrogen oroxygen). Regions of the catalyst layer accessible to these three phasesare referred to as the three-phase boundary. Increasing the three-phaseboundary increases the performance of the fuel cell.

The performance of the PEMFC can decline during use. For example,agglomeration and dissolution of the catalyst particles during thecourse of cycling the fuel cell are a few causes for this decline.Therefore, reducing agglomeration and dissolution is also important forincreasing the performance of the fuel cell.

Additionally, platinum and other suitable noble metal catalysts areexpensive. In order to reduce costs, it is desirable to use low platinumloading electrodes. Low platinum loadings, however, result in high powerperformance losses that exceed that predicted for kinetic activationlosses alone. High performing low platinum loading electrodes cannot beformed by simply reducing the platinum loading of an electrode.

SUMMARY

A membrane electrode assembly includes a membrane, an anode catalystlayer and a cathode catalyst layer. The anode catalyst layer is on afirst side of the membrane and the cathode catalyst layer is on a secondside of the membrane, wherein the second side of the membrane isopposite the first side of the membrane along a first axis. The cathodecatalyst layer includes agglomerates formed of a catalyst supportsupporting catalyst particles, an agglomerate ionomer and aninter-agglomerate ionomer. The agglomerate ionomer surrounds theagglomerates and the inter-agglomerate ionomer is in regions between theagglomerates surrounded by the agglomerate ionomer. The agglomerateionomer is different than the inter-agglomerate ionomer. Methods toproduce the catalyst layer are also provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1a is a perspective view of a fuel cell repeat unit.

FIG. 1b is an enlarged view of a mixed-ionomer cathode catalyst layer ofthe fuel cell repeat unit of FIG. 1 a.

FIG. 2 illustrates a method for forming the mixed-ionomer cathodecatalyst layer of FIG. 1 b.

FIG. 3 is an enlarged schematic view of a mixed-ionomer cathode catalystlayer having an equivalent weight or composition gradient along ahorizontal axis.

FIG. 4 illustrates a method for forming the mixed-ionomer catalyst layerof FIG. 3 having an equivalent weight or composition gradient along thehorizontal axis.

FIG. 5 is an enlarged schematic view of a mixed-ionomer cathode catalystlayer having an equivalent weight or composition gradient in a radialdirection surrounding an agglomerate.

FIG. 6 illustrates a method of forming the mixed-ionomer cathodecatalyst layer of FIG. 5.

DETAILED DESCRIPTION

Fuel cells convert chemical energy to electrical energy using one ormore fuel cell repeat units. The fuel cell repeat unit described hereinincludes a mixed-ionomer catalyst layer. The mixed-ionomer catalystlayer includes an agglomerate ionomer surrounding agglomerates and aninter-agglomerate ionomer between the agglomerates surrounded by theagglomerate ionomer. The mixed-ionomer catalyst layer can be formed ofone or more discrete coatings or layers. The agglomerate ionomer and theinter-agglomerate ionomer of a discrete catalyst layer are different.The mixed-ionomer catalyst layer enables the catalyst layer to befurther tailored to address the unique sources of overpotential for alow catalyst loading electrode. A method of forming the mixed-ionomercatalyst layer is also described.

FIG. 1a illustrates a perspective view of one example fuel cell repeatunit 10, which includes membrane electrode assembly (MEA) 12 (havinganode catalyst layer (CL) 14, membrane 16 and cathode catalyst layer(CL) 18), anode gas diffusion layer (GDL) 20, cathode gas diffusionlayer (GDL) 22, anode flow field 24 and cathode flow field 26. Fuel cellrepeat unit 10 can have coolant flow fields adjacent to anode flow field24 and cathode flow field 26. Coolant flow fields are not illustrated inFIG. 1 a.

Anode GDL 20 faces anode flow field 24 and cathode GDL 22 faces cathodeflow field 26. Anode CL 14 is positioned between anode GDL 20, andmembrane 16 and cathode CL 18 is positioned between cathode GDL 22 andmembrane 16. In one example, fuel cell repeat unit 10 can be a polymerelectrolyte membrane (PEM) fuel cell that uses hydrogen fuel (i.e.,hydrogen gas) and oxygen oxidant (i.e., oxygen gas or air). It isrecognized that fuel cell repeat unit 10 can use alternative fuelsand/or oxidants.

In operation, anode GDL 20 receives hydrogen gas (H₂) by way of anodeflow field 24. Anode CL 14, which contains a catalyst such as platinum,causes the hydrogen molecules to split into protons (H⁺) and electrons(e⁻). The protons and electrons travel to cathode CL 18; the protonspass through membrane 16 to cathode CL 18, while the electrons travelthrough external circuit 28, resulting in a production of electricalpower. Air or pure oxygen (O₂) is supplied to cathode GDL 22 throughcathode flow field 26. At cathode CL 18, oxygen molecules react with theprotons and electrons from anode CL 14 to form water (H₂O), which thenexits fuel cell 10, along with excess heat.

Membrane 16 is a semi-permeable membrane located between anode CL 14 andcathode CL 18. Membrane 16 allows movement of protons and water but doesnot conduct electrons. Protons and water from anode CL 14 can movethrough membrane 16 to cathode CL 18. Membrane 16 can be formed of anionomer. An ionomer is a polymer with ionic properties. In one example,membrane 16 is formed of a perfluorosulfonic acid (PFSA)-containingionomer, such as Nafion® by E.I. DuPont, USA. PFSA polymers are composedof fluorocarbon backbones with sulfonate groups attached to shortfluorocarbon side chains.

In another example, membrane 16 is formed of a hydrocarbon ionomer. Ingeneral, the main chains of hydrocarbon ionomers do not contain largeamounts of fluorine, unlike PFSA ionomers which have highly fluorinatedbackbones. A hydrocarbon ionomer is an ionomer having a main chain whichcontains hydrogen and carbon, and which may also contain a small molefraction of hetero atoms such as oxygen, nitrogen, sulfur, and/orphosphorus. These hydrocarbon ionomers primarily include aromatic andaliphatic ionomers. Examples of suitable aromatic ionomers include butare not limited to sulfonated polyimides, sulfoalkylated polysulfones,poly(β-phenylene) substituted with sulfophenoxy benzyl groups, andpolybenzimidazole ionomers. Non-limiting examples of suitable aliphaticionomers are those based upon vinyl polymers, such as cross-linkedpoly(styrene sulfonic acid), poly(acrylic acid), poly(vinylsulfonicacid), poly(2-acrylamide-2-methylpropanesulfonic acid) and theircopolymers.

The composition of membrane 16 affects the operating temperature of fuelcell repeat unit 10. For example, hydrocarbon ionomers typically have ahigher glass transition temperature than PFSA ionomers, which enables ahydrocarbon ionomer membrane 16 to be operated at a higher temperaturethan a PFSA ionomer membrane 16.

Cathode CL 18 is adjacent to the cathode side of membrane 16. Cathode CL18 is a mixed-ionomer structure that includes two or more ionomers and acatalyst, as described further below. The catalyst of cathode CL 18promotes electrochemical reduction of oxidant (i.e., oxygen). In oneexample, the catalyst is platinum. Cathode CL 18 can have a low platinumloading, such as less than about 0.4 milligrams platinum per squarecentimeter of cathode CL 18. Low platinum loading reduces the fuel cellcosts. However, it has been observed that prior low platinum loadingelectrodes experienced higher oxygen transport losses.

Anode CL 14 is adjacent to the anode side of membrane 16, and oppositecathode CL 18. Anode CL 14 includes one or more ionomers and a catalyst.The catalyst of anode CL 14 promotes electrochemical oxidation of fuel(i.e., hydrogen). Anode CL 14 can have a structure similar to thatdescribed above for cathode CL 18, although anode CL 14 and cathode CL18 can have different compositions. Alternatively, anode CL 14 can beformed of one ionomer and a catalyst.

Fuel cell repeat unit 10 is formed by creating MEA 12 having anode CL 14and cathode CL 18 on either side of membrane 16. Then, MEA 12 iscombined with anode GDL 20 and cathode GDL 22 which have not been coatedwith catalyst. A fuel cell can contain a plurality of fuel cell repeatunits 10 to generate the required electricity. Note that an alternateconfiguration that is used less commonly involves GDL's 20 and 22 coatedwith CL which are then combined with membrane 16. The repeat unitconfiguration is identical to above, and this invention is meant toembody either means of assembling this structure.

MEA 12 can be formed using many different techniques. In one example,MEA 12 can be formed by a decal transfer process in which anode CL 14and cathode CL 18 are formed on substrates and transferred onto membrane16 by hot pressing. Example substrates suitable for a decal transferprocess include Teflon® substrates by E.I. DuPont, USA, and Teflon®derivative substrates. In another example, MEA 12 can be formed bydirectly applying catalyst ink onto membrane 16 to form anode CL 14 andcathode CL 18.

Fuel cell performance losses prevent a fuel cell from operating at itstheoretical efficiency. As discussed above, low catalyst loadingelectrodes generally have performance losses that are higher than thosepredicted based on kinetic activation losses alone. This suggests thatat least one source of overpotential other than kinetics increases withdecreasing catalyst loading. For example, it has been found that oxygentransfer losses are greater in low catalyst loading electrodes, whileohmic losses are lower in thin, low catalyst loading electrodes. Morespecifically, it has been found that oxygen gain rises due to relativehumidity decreases and transport losses are greater for low catalystloading electrodes. The oxygen gain is defined as the difference inperformance measured on oxygen and air on the cathode and an increase inthe oxygen gain usually results from higher oxygen transport losses.

Typically, in a hydrogen-air fuel cell, the hydrogen oxidation reaction(HOR) occurring at anode CL 14 has a relatively lower overpotential at agiven current than the oxidation reduction reaction (ORR) of cathode CL18. Cathode CL 18 having a mixed-ionomer structure and an improvedperformance will be described further, although one skilled in the artwill recognize that anode CL 14 can also have a mixed-ionomer structure.

FIG. 1b is an enlarged schematic view of a portion of membrane 16 andcathode CL 18 which includes agglomerates 30 (having catalyst support 32and catalyst particles 34), agglomerate ionomer 36, inter-agglomerateionomer 38 and water 40. Agglomerate ionomer 36 coats the outer surfaceof agglomerates 30. Inter-agglomerate ionomer 38 forms a structuralsupport system between agglomerates 30. As illustrated, cathode CL 18has a porous structure which enables water 40 to be removed from thesystem and gas to move through cathode CL 18. In this example, cathodeCL 18 is formed of one discrete catalyst layer.

Catalyst supports 32 support catalyst particles 34. In one example,catalyst supports 32 are formed from activated carbon or carbon black,such as Ketjen Black (KB). Catalyst supports 32 have a diameter betweenabout 10 nanometers and about 100 nanometers.

Catalyst particles 34 are deposited on catalyst supports 32. Catalystparticles 34 promote the oxidation reduction reaction (ORR). Forexample, catalyst particles 34 can be a noble metal catalyst, such asruthenium, rhodium, palladium, silver, osmium, iridium, platinum andgold and alloys thereof. To maximize the surface area of availablecatalyst particles 34, catalyst particles 34 can be finely dispersed onthe surface of catalyst supports 32. In one example, agglomerates 30 arecarbon supported platinum particles having 50 weight percent platinumand 50 weight percent carbon (corresponding to a Pt/C ratio of 1:1). ThePt/C ratio can be varied to modify the transport characteristics of thecathode CL.

Agglomerates 30 are individually covered with a film of agglomerateionomer 36. Agglomerate ionomer 36 is a polymer with ionic properties.To maximize the activated catalyst surface area, agglomerates 30 can beformed of a single catalyst support 32 with a plurality of catalystparticles 34 supported thereon. Alternatively, agglomerates 30 can beformed of a plurality of catalyst supports 32 supporting finelydispersed catalyst particles 34. The thickness of the film ofagglomerate ionomer 36 on agglomerates 30 is thin compared to thethickness of cathode CL 18. In one example, cathode CL 18 is betweenabout 5 and about 15 microns thick. In another example, the thickness ofagglomerate ionomer 36 is between about 1 and about 15 nanometers, andmore specifically the thickness of agglomerate ionomer 36 is betweenabout 2 and about 10 nanometers.

Inter-agglomerate ionomer 38 is located at inter-agglomerate regionsbetween agglomerates 30 which are coated with agglomerate ionomer 36.Inter-agglomerate ionomer 38 supports agglomerates 30 such thatagglomerates 30 are dispersed throughout cathode CL 18.Inter-agglomerate ionomer 38 creates a porous structure that enablesreactant gases to permeate CL 18 and water 40 to be removed.Inter-agglomerate ionomer 38 also conducts protons. For example,inter-agglomerate ionomer 38 conducts protons from membrane 16 tocatalyst particles 34.

The optimum amount of ionomer (agglomerate ionomer 36 andinter-agglomerate ionomer 38) depends on the operating conditions of thefuel cell. The weight ratio of agglomerate ionomer 36 tointer-agglomerate ionomer 38 may be not equal. In one example, theagglomerate ionomer to catalyst weight ratio can be between about 0.3and 0.5, and the total ionomer (including agglomerate ionomer 36 andinter-agglomerate ionomer 38) to catalyst weight ratio can be betweenabout 0.5 and 1.1. In another example, the total ionomer to catalystweight ratio can be between about 0.6 and 0.8.

Agglomerate ionomer 36 and inter-agglomerate ionomer 38 have differentequivalent weights (EW) and/or compositions. EW is the ionomer molecularweight that contains 1 mol of ionic groups and indicates the ioniccontent of the ionomer. More specifically, a low EW ionomer has a highionic content relative to a high EW ionomer, and is therefore moreconductive. In cathode CL 18, agglomerate ionomer 36 andinter-agglomerate ionomer 38 of a discrete catalyst layer are different.For example, agglomerate ionomer 36 and inter-agglomerate ionomer 38 canhave different compositions or EWs.

The optimum ionomer composition in cathode CL 18 can vary with position,either through thickness or over active area. In one example,inter-agglomerate ionomer 38 defines the macroscopic ionomer structurewhile agglomerate ionomer 36 defines the microscopic ionomer structure.This enables tailoring of both the macroscopic (e.g., micron-scale) andmicroscopic (e.g., nanometer-scale) ionomer structures.

In a specific example, inter-agglomerate ionomer 38 is a hydrocarbonionomer and agglomerate ionomer 36 is a perfluorosulfonic acid (PFSA)ionomer. An example of a PFSA is Nafion™ from E.I. DuPont, which has aPTFE backbone and a short fluorocarbon-based side chain, whereas thebackbone and side chain of a HC-based ionomer is composed ofhydrocarbons instead of fluorocarbons. Mixtures of hydrocarbons andfluorocarbons in the backbone or side chains are also possible. Inaddition, the ionic groups can be an anion other than sulfonate (e.g.,phosphate) and, more even generally, an ionomer can alternatively be ananion-exchange polymer with cations attached to the polymeric chainsinstead of a cation-exchange polymer with anions attached to thepolymeric chains. In the latter case, an anion-exchange ionomer would beused in an anion-exchange membrane fuel cell (AEMFC).

PFSA ionomers have a high gas permeability, but also a high affinity forplatinum. Thus, although oxygen can permeate easily through the PFSAionomer to catalyst particles 34, catalyst particles 34 also dissolveand move through the PFSA ionomer as ionic species. In contrast to PFSAionomers, hydrocarbon ionomers generally have a low gas permeability anda low solubility for platinum. By coating agglomerates 30 with PFSAagglomerate ionomer 36, reactant gases can easily penetrate PFSAagglomerate ionomer 36 to reach catalyst particles 34. Additionally, bysupporting agglomerates 30 with hydrocarbon inter-agglomerate ionomer38, platinum catalyst particles 34 do not migrate into membrane 16through cathode CL 18. During cycling only small amounts of platinumcatalyst particles 34 are lost into PFSA agglomerate ionomer 36surrounding agglomerates 30. The low solubility of hydrocarboninter-agglomerate ionomer 38 reduces or prevents further migration ofplatinum catalyst particles 34. That is, hydrocarbon inter-agglomerateionomer 38 prevents or reduces platinum migration into the electrode ormembrane 16.

Additionally, hydrocarbon ionomers are thermally and dimensionallystable ionomers so that hydrocarbon inter-agglomerate ionomer 38functions as an effective scaffolding in porous cathode CL 18. Further,hydrocarbon inter-agglomerate ionomer 38 creates a generally fixedporosity at different hydration levels, thus mitigating performancechanges due to changes in relative humidity.

As discussed above, reducing platinum loading (i.e., reducing the numberof catalyst particles 34 in cathode CL 18) reduces the cost of a fuelcell. However, reducing platinum loading results in high powerperformance losses that exceed what would be predicted for activationloss only. Hindered oxygen diffusion through the microscopic ionomerlayer may be responsible for the excess losses. The mixed-ionomercathode CL 18 described above improves the performance of the fuel cell.Hydrocarbon inter-agglomerate ionomer 38 provides adequate protonconductivity and a more stable macroporous gas pore structure. Forexample, the functions of oxygen transport are defined at the gas porelength scales (about 10 to about 100 nanometers) by pores in hydrocarboninter-agglomerate ionomer 38. Further, the relative proximity ofhydrocarbon inter-agglomerate ionomer 38 to platinum catalyst particles34 reduces the driving force for platinum mobility (i.e.,dissolution/sintering). PFSA agglomerate ionomer 36 provides microscopicproton conductivity while maintain high oxygen transport.

In another example, agglomeration ionomer 36 and inter-agglomerationionomer 38 have different EWs. For example, inter-agglomerate ionomer 38can have a lower EW than agglomerate ionomer 36. In a specific example,inter-agglomerate ionomer 38 is a low EW ionomer, such as between about500 and about 900 or between about 750 and about 850, and agglomerateionomer 36 is a high EW ionomer, such as between about 900 and about1300 or between about 1050 and about 1250. The majority of ohmic lossestypically occur on the length scale of the thickness of cathode CL 18,while gas transport losses can be significant on a smaller length scale.Further, oxygen transport losses are typically the limiting process inlow catalyst loading electrodes. Using low EW inter-agglomerate ionomer38 reduces ohmic losses because a low EW ionomer has a higher ionicconductivity. In other cases, mixed-ionomer cathode CL 18 is formed ofhigh EW inter-agglomerate ionomer 38 and low EW agglomerate ionomer 36.

FIG. 2 is a block diagram of method 42 for forming mixed-ionomer cathodeCL 18, which includes forming ionomer-coated agglomerates (process 44)and forming a catalyst layer (process 46).

First, ionomer-coated agglomerates are formed in process 44. Formingionomer-coated agglomerates includes making a catalyst ink (step 48),mixing the catalyst ink (step 50) and drying the catalyst ink to formpowder (step 52). A catalyst ink is formed in step 48 by mixing catalystparticles with an agglomerate ionomer in liquid form (i.e., ionomerdissolved or dispersed in a solvent, such as isopropyl alcohol, andwater). The agglomerate ionomer can be a fluoro-carbon based ionomer,such as Nafion® by E.I. DuPont, USA. As described above, the catalystparticles can be formed of any noble metal or alloy thereof and can besupported on a carbon support structure. For example, 1:1 Pt/C catalystscan be used. The ratio of agglomerate ionomer to catalyst support andthe surface area of the support in the catalyst ink controls theresulting thickness of the agglomerate ionomer film formed on thecatalyst agglomerates. In one example, the agglomerate ionomer tocatalyst support ratio is controlled in step 48 to form an agglomerateionomer film between about 1 to about 15 nanometers. In another example,the agglomerate ionomer to catalyst support ratio is controlled in step48 to form an agglomerate ionomer film between about 2 to about 10nanometers thick.

Next, the catalyst ink is mixed using aggressive mixing procedures toform a dispersion (step 50). The mixing should be sufficient to ensurethat the ionomer interacts and coats at least the surfaces of theagglomerates. For example, the catalyst ink can be mixed usingultrasonic mixing.

The catalyst ink is then dried to remove the solvent and form a catalystpowder (step 52). Drying the catalyst ink forms catalyst agglomerates 30coated with agglomerate ionomer 36 of FIG. 1 b. In one example, thecatalyst ink is dried at a temperature between about 60 and about 80degrees Celsius for between about 30 and about 60 minutes. In anotherexample, the catalyst ink is dried at a higher temperature to anneal theagglomerate ionomer. For example, the catalyst ink can be heated to atemperature such that the agglomerate ionomer flows. In a specificexample, the catalyst ink is heated at a temperature between about 100and about 150 degrees Celsius for between about 30 and about 60 minutes.The agglomerate ionomer to catalyst ratio of the catalyst ink can bevaried to adjust the thickness of the agglomerate ionomer film on theagglomerates.

Next, a catalyst layer is formed in process 46. Forming a catalyst layerincludes grinding the catalyst powder (step 54), making acoated-catalyst ink (step 56), mixing the coated-catalyst ink (step 58)and applying the coated-catalyst ink to a substrate (step 60). In step54, the catalyst powder formed in step 52 is ground. Immediatelyfollowing step 52, the agglomerate ionomer coats the agglomerates andbonds the agglomerates together. The catalyst powder is ground toseparate the catalyst coated agglomerates.

In step 56, a coated-catalyst ink is formed by mixing the groundcatalyst powder with an inter-agglomerate ionomer in a liquid state. Forexample, the inter-agglomerate ionomer can be dispersed/dissolved inwater and alcohol. As described above, the agglomerate ionomer and theinter-agglomerate ionomer are different. For example, the agglomerateionomer and the inter-agglomerate ionomer can have differentcompositions or EWs. The coated-catalyst ink is mixed using anaggressive mixing procedure in step 58 to form a homogenous catalystink. For example, the coated-catalyst ink can be mixed by ultrasonicmixing. The aggressive mixing ensures that the agglomerates are coatedwith the agglomerate ionomer.

The coated-catalyst ink is applied to a substrate in step 60 to form acatalyst layer. In one example, the coated-catalyst ink is applied to aTeflon® substrate, dried, and transferred to the membrane by a decaltransfer process. In another example, the substrate is a membrane sothat the coated-catalyst ink is applied directly to the membrane, suchas by a spraying process. In a third example, the substrate is a gasdiffusion layer. The catalyst layer has the structure shown in FIG. 1 b,wherein catalyst agglomerates 30 are surrounded by a film layer ofagglomerate ionomer 36 and inter-agglomerate ionomer 38 forms a supportstructure to support catalyst agglomerates 30. The inter-agglomerateionomer to catalyst powder ratio can be varied in step 56 to adjust thethickness of the catalyst layer and the ionomer to total weight ratio.In one example, inter-agglomerate ionomer is varied to form a catalystlayer between about 5 and about 15 microns. In another example, thedesired ionomer to catalyst weight ratio is between about 0.5 and about1.1, where the ionomer weight is the weight of all ionomers of thecatalyst layer and total weight is the total weight of the catalystlayer. In a further example, the ionomer to catalyst weight ratio isbetween about 0.6 and about 0.8. Additionally, the weight ratio ofagglomerate ionomer 36 to inter-agglomerate ionomer 38 may be not equal.For example, the agglomerate ionomer to catalyst weight ratio is betweenabout 0.3 and 0.5.

Method 42 enables cathode CL 18 to have a mixed-ionomer structure. Incathode CL 18, agglomerate ionomer 36, which is closest to catalystparticles 34 is different than inter-agglomerate ionomer 38. Thisenables agglomerate ionomer 36 to be tailored to reduce losses occurringon a small length scale and inter-agglomerate ionomer 38 to be tailoredto reduce losses occurring on the length scale of the thickness ofcatalyst layer 18. As discussed above, in one example, agglomerateionomer 36 can be a PFSA ionomer and inter-agglomerate ionomer 38 can bea hydrocarbon ionomer. In another example, inter-agglomerate ionomer 38can be a low EW ionomer and agglomerate ionomer 36 can be a high EWionomer. In a further example, inter-agglomerate ionomer 38 can have ahigher EW or a lower EW than agglomerate ionomer 36.

Method 42 also enables the ratio of agglomerate ionomer 36 tointer-agglomerate ionomer 38 to be adjusted by varying the amount ofcatalyst particles (i.e., carbon-supported platinum particles) toionomer in process 44. In method 42, the composition or EW ofagglomerate ionomer 36 and inter-agglomerate ionomer 38 is constantalong the thickness. However, the EW or composition ofinter-agglomeration ionomer 38 or agglomeration ionomer 36 may varyacross the thickness of cathode CL 18.

FIG. 3 is a schematic of fuel cell repeat unit 100 having a gradientalong the horizontal axis. The gradient can be an EW gradient or acomposition gradient, and the gradient can be in agglomerate ionomer 36and/or inter-agglomerate ionomer 38. FIG. 3 is not to scale and portionsof FIG. 3 have been exaggerated to illustrate the details of fuel cellrepeat unit 100. Fuel cell repeat unit 100 includes membrane 116,cathode CL 118 (having first layer 118 a, second layer 118 b and thirdlayer 118 c), and cathode GDL 122. The anode side of fuel cell repeatunit 100 is not shown.

As illustrated, cathode CL 118 can be formed of a plurality of discretelayers: first layer 118 a includes agglomerates 130 a having catalystsupport 132 a and catalyst particles 134 a, agglomerate ionomer 136 aand inter-agglomerate ionomer 138 a; second layer 118 b includesagglomerates 130 b having catalyst support 132 b and catalyst particles134 b, agglomerate ionomer 136 b and inter-agglomerate ionomer 138 b;and third layer 118 c includes agglomerates 130 c having catalystsupport 132 c and catalyst particles 134 c, agglomerate ionomer 136 cand inter-agglomerate ionomer 138 c.

Within a specific descrete layer of cathode CL 118, agglomerate ionomer136 has a different EW or composition than inter-agglomerate ionomer138, or proportions of agglomerate ionomer 136 and inter-agglomerateionomer 138 may differ. For example, in first layer 118 a, agglomerateionomer 136 a may have a different EW or composition thaninter-agglomerate ionomer 138 a. That is, agglomerate ionomer 136 andinter-agglomerate ionomer 138 of the same discrete layer of cathode CL118 are different.

Further, agglomerate ionomer 136 of each discrete layer 118 a, 118 b,118 c of cathode CL 118 can be different from one another, such ashaving different EWs or compositions. As described further below,agglomerate ionomers 136 a, 136 b and 136 c can form a gradient alongthe horizontal axis of cathode CL 118, where the horizontal axis extendsbetween membrane 116 and cathode GDL 122. Inter-agglomerate ionomer 138can vary between discrete layers of cathode CL 118 in a similar manner.

In a first example, inter-agglomerate ionomers 138 a, 138 b and 138 chave different EWs. For example, inter-agglomerate ionomer 138 a can bea lower EW ionomer than inter-agglomerate ionomer 138 b which is a lowerEW ionomer than inter-agglomerate ionomer 138 c such that cathode CL 118has an EW inter-agglomerate ionomer gradient along the horizontal axis.In this example, the EW of inter-agglomerate ionomer 138 increases alongthe thickness of cathode CL 118 (i.e., the horizontal axis) withincreasing distance from membrane 116. This example configuration isbeneficial because during operation the flux rate of protons is highernear membrane 116 and decreases along the horizontal axis due toconsumption in the fuel-cell reaction. Therefore, improved ionicconductivity in cathode CL 118 is beneficial near membrane 116 andimproved oxygen transport is beneficial near cathode GDL 122.Alternatively, inter-agglomerate ionomer 138 can have a compositiongradient along the horizontal axis.

In a second example, agglomerate ionomers 136 a, 136 b and 136 c aredifferent. For example, agglomerate ionomer 136 a can be a higher EWionomer than agglomerate ionomer 136 b which is a higher EW ionomer thanagglomerate ionomer 136 c such that cathode CL 118 has an EW agglomerateionomer gradient along the horizontal axis. In this example, the EW ofagglomerate ionomer 136 decreases along the thickness of cathode CL 118(i.e., the horizontal axis) with increasing distance from membrane 116.This example configuration is beneficial because during operation theoxygen concentration near membrane 116 is lower than the oxygenconcentration near cathode GDL 122 and, therefore, higher EW agglomerateionomer 136 with higher oxygen permeability (especially under dryconditions) is preferable near membrane 116. Alternatively, agglomerateionomer 136 can have a composition gradient along the horizontal axis.

Cathode CL 118 having a gradient in inter-agglomerate ionomer 138 oragglomerate ionomer 136 is formed according to method 142 of FIG. 4.Method 142 is similar to method 42, except processes 144 and 146 arerepeated after applying the coated-catalyst ink to a substrate. Forexample, a first cathode CL is formed by making a catalyst ink (step148) with catalyst particles and a first agglomerate ionomer. Thecatalyst ink is mixed (step 150) and dried (step 152). In one example,the agglomerate ionomer is varied to create an agglomerate film betweenabout 1 to about 15 nanometers thick. In another example, theagglomerate ionomer is varied to create an agglomerate film between 2 toabout 10 nanometers thick on a 1:1 Pt/C carbon-supported catalyst. Thecatalyst powder containing catalyst particles coated with the firstagglomerate ionomer is ground (step 154) and added to a coated-catalystink containing a first inter-agglomerate ionomer (step 156). Thiscoated-catalyst ink is mixed (158) and applied to a substrate ormembrane (step 160) to form a first catalyst layer.

The process is then repeated to form a second catalyst layer. That is, asecond catalyst ink is formed by mixing a second agglomerate ionomerwith second catalyst particles (step 148). The second catalyst ink ismixed (step 150), dried (step 152) and ground (step 154). In step 156, asecond coated-catalyst ink is formed by mixing the coated-catalystpowder of step 154 with a second inter-agglomerate ionomer. The secondcoated-catalyst ink is mixed (step 158) and applied to the substrate ontop of the first catalyst layer (step 160). The ionomer (includingagglomerate ionomer and inter-agglomerate ionomer) to catalyst weightratio of each catalyst ink can be varied to control the weight ratio ofionomer to total weight of the cathode catalyst layer. In one example,the ionomer to catalyst weight ratio of the cathode catalyst layer isbetween about 0.5 and about 1.1. In another example, the ionomer tocatalyst weight ratio of the cathode catalyst layer is between about 0.6and 0.8 for a low loading electrode. The weight ratio of agglomerateionomer 136 to inter-agglomerate ionomer 138 may be not equal. Inanother example, the amount of inter-agglomerate ionomer can be variedto create a cathode catalyst layer having a thickness between about 5and about 15 microns.

The method of forming the cathode CL 118 on membrane 116 affects theorder in which the cathode layers are formed. For example, when cathodeCL 118 is formed using a decal transfer method, the last catalyst layerformed is adjacent membrane 116, while when a spray method is used, thelast catalyst layer formed is adjacent cathode GDL 122.

To form gradients in cathode CL 118, first and second inter-agglomerateionomers or first and second agglomerate ionomers are different alongthe horizontal axis of cathode CL 118. More specifically, to formcathode CL 118 having an inter-agglomerate gradient in the thicknessdirection of cathode CL 118 (i.e., along the horizontal axis), first andsecond catalyst particles and agglomerate ionomers are the same, andfirst and second inter-agglomerate ionomers are different. To formcathode CL 118 having an agglomerate gradient in the thickness directionof cathode CL 118 (i.e., along the horizontal axis), first and secondcatalyst particles and inter-agglomerate ionomers are the same and firstand second agglomerate ionomers are different.

Further, method 142 can be used to form cathode CL 118 having a varyingweight ratio of agglomerate ionomer to inter-agglomerate ionomer alongthe thickness of cathode CL 118. Such a cathode CL 118 can be formed byadjusting the amount of inter-agglomerate ionomer added in step 156 foreach catalyst layer 118 a, 118 b, 118 c.

As shown in FIG. 5, agglomerate ionomer 236 can have a gradient in theradial direction from the center of agglomerate 230 (i.e., in thethickness direction of agglomerate ionomer 236). In FIG. 5, agglomerateionomer 236 includes first agglomerate ionomer 236 a and secondagglomerate ionomer 236 b. First agglomerate ionomer 236 a is adjacentcatalyst support 232 and catalyst particles 234; second agglomerateionomer 236 b is adjacent first agglomerate ionomer 236 a andinter-agglomerate ionomer 238. In one example, first agglomerate ionomer236 a and second agglomerate ionomer 236 b have different compositions.In another example, first agglomerate ionomer 236 a and secondagglomerate ionomer 236 b have different EWs. Additionally, agglomerateionomers 236 a and 236 b can be different than inter-agglomerate ionomer238.

Agglomerate ionomer 236 having a gradient in the radial direction can beformed according to method 242 of FIG. 6. Method 242 is similar tomethod 42 of FIG. 2 except process 244 is repeated to form a pluralityof layers of agglomerate ionomer on the catalyst particles beforeforming the coated-catalyst ink. For example, a first catalyst ink isformed in step 248 by mixing catalyst particles with a first agglomerateionomer. The first catalyst ink is mixed (step 250) and dried (step252).

The process of making ionomer-coated agglomerates (step 244) is thenrepeated using the catalyst powder formed in step 252. The catalystpowder of step 252 is added to a second agglomerate ionomer to form acatalyst ink (step 248), which is mixed (step 250) and dried (step 252).The resulting powder contains catalyst agglomerates with two agglomerateionomer films. In one example, the catalyst agglomerates are 1:1 Pt/Ccatalysts with the two agglomerate ionomer films combined having athickness of between about 1 to about 15 nanometers. In another example,the catalyst agglomerates are 1:1 Pt/C catalysts with the twoagglomerate ionomer films combined having a thickness of between about 2to about 10 nanometers.

The dried powder containing agglomerates with two agglomerate ionomerlayers is then ground (step 254) and added to a first inter-agglomerateionomer to form a first coated-catalyst ink (step 256). The firstcoated-catalyst ink is mixed (step 258) and applied to a substrate (step260) to form a cathode CL. The ionomer at each catalyst ink step can bevaried to control the ionomer to total weight ratio of the cathodecatalyst layer, and the weight ratio of agglomerate ionomer 236 tointer-agglomerate ionomer 238 may be not equal. In one example, theagglomerate ionomer to catalyst ratio is between about 0.3 and 0.5, andthe ionomer (including agglomerate and inter-agglomerate) to catalystweight ratio is between about 0.5 and 1.1. In another example that isfavorable at low catalyst loadings, the ionomer to catalyst weight ratiois between about 0.6 and 0.8. Additionally, the amount ofinter-agglomerate ionomer can be varied to control the thickness of thecathode catalyst layer. For example, the total thickness of the cathodecatalyst layer can be between about 5 and about 15 microns.

Method 242 enables a plurality of thin agglomerate ionomer films orlayers to be formed on the agglomerates. This enables the agglomerateionomer composition and/or EW to be varied with radial position.Although the term radial has been used above, the agglomerates may notbe spherical. The term radial is used to indicate the direction ofthickness of the agglomerate ionomer.

Forming cathode CL 18, 118, 218 according to method 42, 142, 242,respectively, provides a mixed-ionomer electrode. Cathode CL 18, 118,218 contains agglomerates 30, 130, 230 surrounded by a film ofagglomerate ionomer 36, 136, 236 and an inter-agglomerate ionomer 38,138, 238 between the agglomerate ionomer coated agglomerates. Cathode CL18, 118, 218 is formed of one or more discrete layers. Within a discretelayer, agglomerate ionomer 36, 136, 236 is a different ionomer thaninter-agglomerate ionomer 38, 138, 238. For example, within a discretelayer, agglomerate ionomer 36, 136, 236 has a different composition orEW than inter-agglomerate ionomer 38, 138, 238. Methods 42, 142, 242also enable the ratio of ionomer content in the agglomerate andinter-agglomerate regions to also be controlled.

Where cathode CL 118 is formed of a plurality of discrete catalystlayers, agglomerate ionomer 136 and inter-agglomerate ionomer 138 of thesame discrete catalyst layer have a different composition and/or EW. Asdiscussed above, cathode CL 118, 218 can have a gradient ofinter-agglomerate ionomer EW or composition across the thickness ofcathode CL 118, a gradient of agglomerate ionomer EW or compositionacross the thickness of cathode CL 118, a gradient of agglomerateionomer EW or composition across the thickness of agglomerate ionomer236, a varying agglomerate ionomer to inter-agglomerate ionomer weightratio across the thickness of cathode CL 118 or a combination thereof.

Cathode CL 18, 118, 218 enables a low catalyst loading electrode to heformed (i.e., less than about 0.1 mg platinum per square centimeter ofelectrode). Cathode Cl. 18, 118, 218 is tailored to reduceover-potential losses specific to low catalyst loading electrodes. Forexample, agglomerate ionomer 36, 136, 236 and inter-agglomerate ionomer38, 138, 238 are varied to reduce transport losses and increase fuelcell performance.

While the invention has been described with reference to an exemplaryembodiment(s), it will be understood by those skilled in the art thatvarious changes may be made and equivalents may be substituted forelements thereof without departing from the scope of the invention. Inaddition, many modifications may be made to adapt a particular situationor material to the teachings of the invention without departing from theessential scope thereof. Therefore, it is intended that the inventionnot be limited to the particular embodiment(s) disclosed, but that theinvention will include all embodiments falling within the scope of theappended claims.

1. A method of forming a catalyst layer for a membrane electrodeassembly, the method comprising: forming a catalyst ink with a catalystand a first ionomer in a liquid dispersed form; drying the catalyst inkto form a coated-catalyst powder; grinding the coated-catalyst powder;forming a coated-catalyst ink with the ground coated-catalyst powder anda second ionomer, wherein the second ionomer has a different compositionor equivalent weight than the first ionomer; and applying thecoated-catalyst ink to a substrate to form a catalyst layer.
 2. Themethod of claim 1 wherein the first ionomer is a PFSA ionomer and thesecond ionomer is a hydrocarbon ionomer.
 3. The method of claim 1wherein the first ionomer has a different composition than the secondionomer.
 4. The method of claim 1 wherein the first ionomer has adifferent equivalent weight ionomer than the second ionomer.
 5. Themethod of claim 1, further comprising: forming a second catalyst inkwith the catalyst and a third ionomer in a liquid dispersed form; dryingthe second catalyst ink to form a second coated-catalyst powder;grinding the second coated-catalyst powder; forming a secondcoated-catalyst ink with the ground second coated-catalyst powder and afourth ionomer, wherein the second ionomer has a different compositionor equivalent weight than the fourth ionomer; and applying the secondcoated-catalyst ink onto the catalyst layer.
 6. The method of claim 1,further comprising: forming a second catalyst ink with the catalyst anda third ionomer in a liquid dispersed form, wherein the third ionomerhas a different composition or equivalent weight than the first ionomer;drying the second catalyst ink to form a second coated-catalyst powder;grinding the second coated-catalyst powder; forming a secondcoated-catalyst ink with the ground second coated-catalyst powder and afourth ionomer; and applying the second coated-catalyst ink onto thecatalyst layer.
 7. The method of claim 1, further comprising: prior togrinding the coated-catalyst powder, forming an intermediate catalystink with the coated-catalyst powder and an intermediate ionomer in aliquid dispersed form; and drying the intermediate catalyst ink suchthat the resulting coated-catalyst powder to be subsequently groundcomprises a plurality of ionomer films.
 8. The method of claim 1 whereinthe catalyst includes catalyst particles supported on catalyst supports,and further comprising: controlling a ratio of the first ionomer to thecatalyst support to form an ionomer film between about 1 to about 15nanometers.
 9. The method of claim 1 wherein the catalyst includescatalyst particles supported on catalyst supports, and furthercomprising: controlling a ratio of the first ionomer to the catalystsupport to form an ionomer film between about 2 to about 10 nanometers.10. The method of claim 1 wherein drying the catalyst ink to form thecoated-catalyst powder includes heating the catalyst ink at atemperature between about 100 and about 150 degrees Celsius for betweenabout 30 and about 60 minutes.
 11. The method of claim 1, furthercomprising: controlling a ratio of the second ionomer to the groundcoated-catalyst powder to form the catalyst layer with a thicknessbetween about 5 and about 15 microns.
 12. A method of forming a catalystlayer for a membrane electrode assembly, the method comprising: forminga catalyst ink with a catalyst and an agglomerate ionomer in a liquiddispersed form; drying the catalyst ink to form a coated-catalystpowder; grinding the coated-catalyst powder; forming a coated-catalystink with the ground coated-catalyst powder and an inter-agglomerateionomer, wherein the inter-agglomerate ionomer has a differentcomposition or equivalent weight than the agglomerate ionomer; andapplying the coated-catalyst ink to a substrate to form a catalyst layercomprising a plurality of agglomerates surrounded by and in directcontact with the agglomerate ionomer and with the inter-agglomerateionomer provided in regions between the agglomerates and in contact withthe agglomerate ionomer surrounding the agglomerates such that theinter-agglomerate ionomer supports the agglomerate ionomer coveredagglomerates in a dispersed manner throughout the catalyst layer.